US4464478A - Catalyst components and catalysts for polymerizing olefins - Google Patents

Catalyst components and catalysts for polymerizing olefins Download PDF

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Publication number
US4464478A
US4464478A US06/428,976 US42897682A US4464478A US 4464478 A US4464478 A US 4464478A US 42897682 A US42897682 A US 42897682A US 4464478 A US4464478 A US 4464478A
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compounds
electron
reaction
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Umberto Scata
Enrico Albizzati
Enzo Giannetti
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Montedison SpA
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Montedison SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts

Definitions

  • Our group has disclosed catalysts useful in the polymerization of alpha-olefins and prepared by reacting a Ti compound and an electron-donor compound with a carrier based on Mg dihalide obtained by reaction of an organometallic Mg compound containing OR groups bound to the Mg atom, with a halogenating agent other than the halogenated Ti compounds, and capable of converting, at least partially, the organometallic Mg compound into a dihalide.
  • Said catalysts give very high polymer yields with respect to the Ti compound contained in the catalyst. In some cases, however, such yields are not satisfactory if referred to the halide which is present in the halogenated compounds constituting the catalyst, since too high contents of halogenated compounds in the polymer are not desirable as they bring about corrosion phenomena in the apparatuses utilized for processing the polymer.
  • One object of this invention is to provide new catalyst-forming components comprising a carrier based on Mg dihalide and which have improved characteristics as compared with the aforesaid previously disclosed catalyst-forming components.
  • Another object is to provide catalysts prepared from the new components and which polymerize olefins to high yields of polymers having a reduced content of halogenated compounds liable to corrode the apparatuses used in processing the polymers.
  • the remaining valence of the Mg is satisfied by a halogen, a radical R or OR as defined, or by COX' in which X' is halogen.
  • the compound (HED) used in practicing this invention is selected from the aliphatic, cycloaliphatic or aromatic alcohols or thioalcohols having 1 to 20 C, the phenols having 6 to 20 C and the silanols containing 1 to 20 C, and is employed in such amounts as to result in an adduct, with the Mg dihalide, containing from 0.1 to 6.0 moles of (HED) per mole of the dihalide.
  • the complex between Mg dihalide and (ED) employed in (c) contains up to 6 moles of (ED) compound per mole of Mg dihalide, and the (ED) compound preferably contains one or more electronegative groups containing oxygen atoms.
  • the (ED) compound is an alkyl ether, such as, for instance, ethyl ether, n-butyl ether, isoamyl ether.
  • reaction products between at least one Mg dihalide, a Ti compound and an (ED) compound, in which the ratio between moles of (ED) and gram atoms of Ti ranges from 0.2 to 4.
  • the compounds, other than the Mg dihalides, used for preparing the present catalyst components have the general formula:
  • Presently preferred compounds of formula R m MgX n are the Mg-monoalkyls and Mg-phenyls, the Mg-mono and -dialcoholates and the Mg-dialkyls, specific examples of which include: n-butyl-magnesium-chloride, phenylmagnesium-chloride, n-butylmagnesium-butoxy, n-propyl-magnesium-propoxy, sec.-butylmagnesium-chloride, magnesium diethyl, benzyl-magnesium-chloride Mg(OC 2 H 5 ) 2 , ClMgOC 2 H 5 , ClMgOC 6 H 5 and ClMgOSi(C 6 H 5 ) 3 .
  • Said Mg compounds can be utilized as such or in the form of complexes with ethers or amines, (examples of which complexes are described in British Pat. No. 1,343,781), or with organometallic compounds of elements such as Al, Zn, B, Si, or with metal alcoholates such as Ti- and Zr-tetraalcoholates and Al-alcoholates. Such compounds are reacted preferably, in the form of solutions in hydrocarbons or of complexes thereof which are hydrocarbon-soluble.
  • n is preferably comprised between 0.15 and 2.5 and R is a hydrocarbon radical having 1 to 20 C, in particular an alkyl radical having 2 to 12 C, are of particular interest due to the possibility of obtaining catalyst components having a narrow particle distribution by the use thereof.
  • Such complexes are generally prepared by reacting, according to conventional methods, metal Mg with an organic halide employed in a stoichiometric amount, and successively with the AlR 3 compound.
  • organometallic Mg-compounds R m MgX n are converted to Mg-dihalide are known in the literature. They consist in reacting the R m MgX n compound with a halogenating agent capable of introducing Mg-halogen bonds into the organometallic Mg compound.
  • Examples of the useful halogenating agents are: SiCl 4 , halosilanes such as ClSi(CH 3 ) 3 , Cl 3 SiCH 3 , SOCl 2 , Al-alkyl halides such as Al(C 2 H 5 ) 2 Cl, Al(C 2 H 5 )Cl, halides such as AlCl 3 , AlBr 3 , SnCl 4 , BF 3 , BCl 3 , SbCl 3 , ZnCl 2 , hydrogen halides such as hydrogen chloride, alkyl or aryl halides such as dichloroethane, chlorobenzene, CCl 4 .
  • the amount of halogenating agent used must be such as to convert the organometallic Mg-compound to the dihalide in amounts higher than 10%.
  • the halogenating agent can be reacted with compound R m MgX n either after formation of the latter or during formation thereof.
  • the decomposition product of the Mg compound is preferably reacted with the (HED) compound; the latter, however, can be reacted during the decomposition reaction of the Mg compound.
  • the reaction with the (HED) compound is advantageously conducted in the presence of the (ED) compound. The latter, however, can be reacted either before or after or, as already stated, during the reaction between the Ti compound and product (c).
  • the complex of this invention is prepared by decomposing the R m MgX n compound or complexes thereof with an (ED) compound, to obtain a product consisting of or including a Mg dihalide or complexes thereof with ethers, then reacting said product with the (HED) compound and the (ED) compound, and then with the Ti compound.
  • the reaction between the Ti compound, preferably TiCl 4 , and the adduct of the Mg dihalide with at least one (HED) compound may be carried out using the adduct in suspension or in solution in a hydrocarbon diluent.
  • silanols useful to prepare the catalyst component have the formula:
  • R is an alkyl, cycloalkyl or aryl group having 1 to 18 C, and 1 ⁇ n ⁇ 3.
  • Specific examples of these compounds are: trimethylsilanol, triphenylsilanol, diphenyldisilanol and butyltrisilanol.
  • Catalysts for the polymerization of olefins are obtained from the catalytic components of this invention by reacting said components with organometallic Al-compounds, for example Al-trialkyls, such as Al(C 2 H 5 ) 3 , Al(i-C 4 H 9 ) 3 , Al alkyl halides such as Al(C 2 H 5 ) 2 Cl, or compounds R 2 Al-O-AlR 2 , or mixtures of such aluminum compounds with organometallic Mg compounds, such as Mg-dialkyls or Mg-alkyl-alkoxy compounds.
  • organometallic Al-compounds for example Al-trialkyls, such as Al(C 2 H 5 ) 3 , Al(i-C 4 H 9 ) 3 , Al alkyl halides such as Al(C 2 H 5 ) 2 Cl, or compounds R 2 Al-O-AlR 2 , or mixtures of such aluminum compounds with organometallic Mg compounds, such as Mg
  • the Al/Ti ratio is comprised in a wide range, for example between 1 and 1000.
  • the Al alkyl compound is not reacted with the electron-donor compound, or the latter is employed in limited amounts, lower than 0.3 moles per mole of Al alkyl compound.
  • the polymerization of olefins and of mixtures thereof is carried out according to known methods, by operating in the liquid phase either in the presence or the absence of an inert hydrocarbon solvent, or in the gas phase.
  • the polymerization temperature generally ranges from 50° to 150° C. and the pressure is either atmospheric or higher.
  • Example 1 was repeated, but using [Mg(n-C 4 H 9 ) 2 ] 2 . Al(i-C 4 H 9 ) 3 in a 1.33M heptane solution.
  • Example 1 was repeated but using a 0.66M solution of [Mg(n-C 4 H 9 ) 2 ] 2 .Al(i-C 4 H 9 ) 3 .
  • the solid was separated by filtration after 4 washings with 200 ml portions of n-heptane at 50° C., whereupon it was suspended in 42.4 ml of an 0.5M ethyl benzoate solution in n-heptane and allowed to react for 2 hours at 60° C.
  • the solid was mixed with 53 ml of a 1M heptane solution of n-C 4 H 9 OH and reacted at 60° C. for 2 hours. After 3 washings with 200 ml portions of n-heptane at the same temperature, the solid was suspended in 200 ml of TiCl 4 and heated to 100° C. for 2 hours. The TiCl 4 was removed by filtration and an equal amount thereof was added again. After 2 hours, the mass was filtered and washed with n-heptane at 90° C. until chlorine ions disappeared from the filtrate.
  • Example 6 was repeated, with the exception that 77 ml of a 1.39M solution of the complex (n-C 4 H 9 )MgCl.2.29(n-C 4 H 9 ) 2 O in toluene were dropped into 300 ml of a 1.43M solution of Al(C 2 H 5 )Cl 2 in n-hexane. The temperature was maintained at 25° C. for 3 hours.
  • the solid thus formed was separated by filtration and washed with n-heptane at 50° C., then suspended in 500 ml of n-heptane containing ethyl benzoate and ethanol in amounts respectively equal to 0.2 mole and 3 moles per gram atom of Mg.
  • the reaction with TiCl 4 was effected under the conditions of Example 6.
  • the solid reaction product was separated by filtration and successively treated for 2 hours with 200 ml of TiCl 4 at 135° C. That mass was hot filtered, and 200 ml of TiCl 4 were added to the solid, the mix being kept at 135° C. for 2 hours, hot-filtered and washed with n-heptane until the disappearance of chlorine ions.
  • Example 9 was repeated, but using the reagents indicated in Table II, which also records the results obtained from the polymerization of propylene.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US06/428,976 1978-10-23 1982-09-30 Catalyst components and catalysts for polymerizing olefins Expired - Lifetime US4464478A (en)

Applications Claiming Priority (2)

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IT28994A/78 1978-10-23
IT28994/78A IT1099416B (it) 1978-10-23 1978-10-23 Componenti e catalizzatori per la polimerizzazione delle olefine

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US (1) US4464478A (en, 2012)
JP (1) JPS5558207A (en, 2012)
AT (1) AT365206B (en, 2012)
AU (1) AU534511B2 (en, 2012)
BE (1) BE879507A (en, 2012)
CA (1) CA1131202A (en, 2012)
DE (1) DE2942829A1 (en, 2012)
ES (1) ES485256A1 (en, 2012)
FR (1) FR2439795A1 (en, 2012)
GB (1) GB2033409B (en, 2012)
IT (1) IT1099416B (en, 2012)
NL (1) NL187398B (en, 2012)
NO (1) NO157178C (en, 2012)
ZA (1) ZA795619B (en, 2012)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511703A (en) * 1982-06-24 1985-04-16 Bp Chimie Societe Anonyme Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalysts
US4550095A (en) * 1983-08-30 1985-10-29 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4551440A (en) * 1983-08-30 1985-11-05 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4552858A (en) * 1983-08-30 1985-11-12 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4613581A (en) * 1982-12-28 1986-09-23 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins P-998
US4625003A (en) * 1983-08-30 1986-11-25 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins (P-1026)
US4652541A (en) * 1983-08-30 1987-03-24 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4654318A (en) * 1984-02-28 1987-03-31 Toa Nenryo Kogyo Kabushiki Kaisha Process for preparing catalyst component for polymerization of olefins
US4670525A (en) * 1979-04-01 1987-06-02 Stamicarbon B.V. Catalytic titanium compound, process for the manufacture thereof, and method for the polymerization of alkenes-1 with application of such a titanium component
US4870040A (en) * 1987-11-24 1989-09-26 Shell Oil Company Olefin polymerization catalysts from soluble magnesium alkoxides made from alkyl or aryl magnesium mixed with a branched or aromatic aldehyde
US4870039A (en) * 1987-11-24 1989-09-26 Shell Oil Company Olefin polymerization catalysts from soluble magnesium alkoxides made from mixed magnesium alkyls and aryls
US4980329A (en) * 1986-11-10 1990-12-25 Himont Incorporated Catalyst component and catalyst for the polymerization of alpha-olefins to stereoregular polymers having narrow molecular weight distribution
US5106807A (en) * 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US5349033A (en) * 1986-06-14 1994-09-20 Hoechst Aktiengesellschaft Process for the preparation of polyolefin
US5767031A (en) * 1995-06-07 1998-06-16 Fina Technology, Inc. Ziegler-Natta catalysts modified with metallocenes
US6777508B1 (en) 1980-08-13 2004-08-17 Basell Poliolefine Italia S.P.A. Catalysts for the polymerization of olefins

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56161406A (en) * 1980-05-17 1981-12-11 Mitsubishi Petrochem Co Ltd Polymerization of ethylene
IT1141295B (it) * 1980-04-22 1986-10-01 Montedison Spa Componenti e catalizzatori per la polimerizzazione delle alfaolefine
FR2495162B1 (fr) * 1980-12-02 1985-09-27 Charbonnages Ste Chimique Catalyseur de polymerisation de l'ethylene comprenant un compose aromatique du silicium
JPS57205407A (en) * 1981-06-11 1982-12-16 Toyo Sutoufuaa Chem:Kk Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin
JPS57205408A (en) * 1981-06-11 1982-12-16 Toyo Sutoufuaa Chem:Kk Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin
JPS57205406A (en) * 1981-06-11 1982-12-16 Toyo Sutoufuaa Chem:Kk Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin
JPS57205409A (en) * 1981-06-11 1982-12-16 Toyo Sutoufuaa Chem:Kk Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin
EP0085231B1 (en) * 1981-12-17 1986-11-12 Imperial Chemical Industries Plc Catalyst composition, production and use
FR2529206A1 (fr) * 1982-06-24 1983-12-30 Bp Chimie Sa Procede de preparation de supports a base de chlorure de magnesium pour la preparation de catalyseurs de polymerisation des alpha-olefines et supports obtenus
FR2529207A1 (fr) * 1982-06-24 1983-12-30 Bp Chimie Sa Procede pour la preparation de supports de catalyseurs pour la polymerisation des alpha-olefines et supports obtenus
IT1195953B (it) * 1982-09-10 1988-11-03 Montedison Spa Componenti e catalizzatori per la polimerizzazione di olefine
JPS59145203A (ja) * 1983-02-08 1984-08-20 Toho Titanium Co Ltd オレフィン類重合用触媒成分の製造方法
FR2546522B1 (fr) * 1983-05-25 1985-07-26 Ato Chimie Procede de preparation d'une composante de metal de transition pour un systeme catalytique de polymerisation d'olefines
JPS60115603A (ja) * 1983-11-29 1985-06-22 Toa Nenryo Kogyo Kk オレフインの重合方法
EP0693524B1 (en) * 1994-07-20 1998-06-10 Idemitsu Petrochemical Co., Ltd. Polypropylene resin and film prepared therefrom

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076924A (en) * 1974-09-03 1978-02-28 Mitsui Petrochemical Industries Ltd. Process for polymerization or copolymerizing olefins containing at least 3 carbon atoms
US4115319A (en) * 1975-09-19 1978-09-19 Montedison S.P.A. Catalysts and catalyst components for polymerizing olefins
US4143223A (en) * 1976-03-01 1979-03-06 Mitsui Petrochemical Industries Ltd. Process for polymerizing alpha-olefins and catalyst therefor
US4189553A (en) * 1976-12-01 1980-02-19 The Dow Chemical Company High efficiency catalyst for polymerizing olefins

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2640679A1 (de) * 1976-09-09 1978-03-16 Montedison Spa Katalysatoren und katalysatorkomponenten zur polymerisation von olefinen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076924A (en) * 1974-09-03 1978-02-28 Mitsui Petrochemical Industries Ltd. Process for polymerization or copolymerizing olefins containing at least 3 carbon atoms
US4115319A (en) * 1975-09-19 1978-09-19 Montedison S.P.A. Catalysts and catalyst components for polymerizing olefins
US4143223A (en) * 1976-03-01 1979-03-06 Mitsui Petrochemical Industries Ltd. Process for polymerizing alpha-olefins and catalyst therefor
US4189553A (en) * 1976-12-01 1980-02-19 The Dow Chemical Company High efficiency catalyst for polymerizing olefins

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670525A (en) * 1979-04-01 1987-06-02 Stamicarbon B.V. Catalytic titanium compound, process for the manufacture thereof, and method for the polymerization of alkenes-1 with application of such a titanium component
US6777508B1 (en) 1980-08-13 2004-08-17 Basell Poliolefine Italia S.P.A. Catalysts for the polymerization of olefins
US4511703A (en) * 1982-06-24 1985-04-16 Bp Chimie Societe Anonyme Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalysts
US4673662A (en) * 1982-06-24 1987-06-16 Bp Chemicals Limited Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalysts
US4613581A (en) * 1982-12-28 1986-09-23 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins P-998
US4686265A (en) * 1982-12-28 1987-08-11 Toa Nenryo Kogyo Kabushiki Kaisha Process for polymerization of olefins
US4550095A (en) * 1983-08-30 1985-10-29 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4551440A (en) * 1983-08-30 1985-11-05 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4552858A (en) * 1983-08-30 1985-11-12 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4588793A (en) * 1983-08-30 1986-05-13 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4625003A (en) * 1983-08-30 1986-11-25 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins (P-1026)
US4652541A (en) * 1983-08-30 1987-03-24 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst component for polymerization of olefins
US4654318A (en) * 1984-02-28 1987-03-31 Toa Nenryo Kogyo Kabushiki Kaisha Process for preparing catalyst component for polymerization of olefins
US5349033A (en) * 1986-06-14 1994-09-20 Hoechst Aktiengesellschaft Process for the preparation of polyolefin
US4980329A (en) * 1986-11-10 1990-12-25 Himont Incorporated Catalyst component and catalyst for the polymerization of alpha-olefins to stereoregular polymers having narrow molecular weight distribution
US4870039A (en) * 1987-11-24 1989-09-26 Shell Oil Company Olefin polymerization catalysts from soluble magnesium alkoxides made from mixed magnesium alkyls and aryls
US4870040A (en) * 1987-11-24 1989-09-26 Shell Oil Company Olefin polymerization catalysts from soluble magnesium alkoxides made from alkyl or aryl magnesium mixed with a branched or aromatic aldehyde
US5106807A (en) * 1990-01-10 1992-04-21 Himont Incorporated Components and catalysts for the polymerization of olefins
US5767031A (en) * 1995-06-07 1998-06-16 Fina Technology, Inc. Ziegler-Natta catalysts modified with metallocenes

Also Published As

Publication number Publication date
NO793365L (no) 1980-04-24
NL7907704A (nl) 1980-04-25
FR2439795A1 (fr) 1980-05-23
JPS5558207A (en) 1980-04-30
ZA795619B (en) 1980-10-29
AU5194279A (en) 1980-05-01
JPS6363562B2 (en, 2012) 1988-12-07
GB2033409A (en) 1980-05-21
ATA686379A (de) 1981-05-15
GB2033409B (en) 1983-09-01
CA1131202A (en) 1982-09-07
BE879507A (fr) 1980-04-21
FR2439795B1 (en, 2012) 1985-03-01
AT365206B (de) 1981-12-28
DE2942829A1 (de) 1980-04-30
NO157178B (no) 1987-10-26
NL187398B (nl) 1991-04-16
AU534511B2 (en) 1984-02-02
IT1099416B (it) 1985-09-18
DE2942829C2 (en, 2012) 1991-05-16
NO157178C (no) 1988-02-03
IT7828994A0 (it) 1978-10-23
ES485256A1 (es) 1980-07-01

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